JP7375749B2 - Polyamide-imide resin, polyamide-imide varnish and polyamide-imide film - Google Patents
Polyamide-imide resin, polyamide-imide varnish and polyamide-imide film Download PDFInfo
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- JP7375749B2 JP7375749B2 JP2020518223A JP2020518223A JP7375749B2 JP 7375749 B2 JP7375749 B2 JP 7375749B2 JP 2020518223 A JP2020518223 A JP 2020518223A JP 2020518223 A JP2020518223 A JP 2020518223A JP 7375749 B2 JP7375749 B2 JP 7375749B2
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- polyamide
- imide
- mol
- film
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- 239000004962 Polyamide-imide Substances 0.000 title claims description 110
- 229920002312 polyamide-imide Polymers 0.000 title claims description 110
- 239000011347 resin Substances 0.000 title claims description 55
- 229920005989 resin Polymers 0.000 title claims description 55
- 239000002966 varnish Substances 0.000 title claims description 43
- 150000001875 compounds Chemical class 0.000 claims description 86
- 150000004985 diamines Chemical class 0.000 claims description 31
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 29
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 26
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 34
- 239000002253 acid Substances 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 21
- 238000000034 method Methods 0.000 description 20
- 239000002904 solvent Substances 0.000 description 17
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 16
- 229920001721 polyimide Polymers 0.000 description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 239000000126 substance Substances 0.000 description 14
- 239000007810 chemical reaction solvent Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- -1 aromatic dicarbonyl compound Chemical class 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 11
- 239000011521 glass Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 8
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 7
- 238000007112 amidation reaction Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- OVASAEXSPYGGES-UHFFFAOYSA-N C1C2C(C(OC3=O)=O)C3C1CC2(C1=O)CCC21CC1CC2C2C(=O)OC(=O)C12 Chemical compound C1C2C(C(OC3=O)=O)C3C1CC2(C1=O)CCC21CC1CC2C2C(=O)OC(=O)C12 OVASAEXSPYGGES-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 125000002723 alicyclic group Chemical group 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 6
- 239000000470 constituent Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 3
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 2
- JYYNAJVZFGKDEQ-UHFFFAOYSA-N 2,4-Dimethylpyridine Chemical compound CC1=CC=NC(C)=C1 JYYNAJVZFGKDEQ-UHFFFAOYSA-N 0.000 description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 241001272720 Medialuna californiensis Species 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 150000004694 iodide salts Chemical class 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- BEBFJOSPYYGOKL-UHFFFAOYSA-N (3-ethylphenyl)methanamine Chemical compound CCC1=CC=CC(CN)=C1 BEBFJOSPYYGOKL-UHFFFAOYSA-N 0.000 description 1
- RGXUCUWVGKLACF-UHFFFAOYSA-N (3-methylphenyl)methanamine Chemical compound CC1=CC=CC(CN)=C1 RGXUCUWVGKLACF-UHFFFAOYSA-N 0.000 description 1
- OLQWMCSSZKNOLQ-ZXZARUISSA-N (3s)-3-[(3r)-2,5-dioxooxolan-3-yl]oxolane-2,5-dione Chemical compound O=C1OC(=O)C[C@H]1[C@@H]1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-ZXZARUISSA-N 0.000 description 1
- RCNBXBQGBCGTPB-UHFFFAOYSA-N (4-dodecylphenyl)methanamine Chemical compound CCCCCCCCCCCCC1=CC=C(CN)C=C1 RCNBXBQGBCGTPB-UHFFFAOYSA-N 0.000 description 1
- DGAGEFUEKIORSQ-UHFFFAOYSA-N (4-ethylphenyl)methanamine Chemical compound CCC1=CC=C(CN)C=C1 DGAGEFUEKIORSQ-UHFFFAOYSA-N 0.000 description 1
- HMTSWYPNXFHGEP-UHFFFAOYSA-N (4-methylphenyl)methanamine Chemical compound CC1=CC=C(CN)C=C1 HMTSWYPNXFHGEP-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- CGSKOGYKWHUSLC-UHFFFAOYSA-N 1-(4-aminophenyl)-1,3,3-trimethyl-2h-inden-5-amine Chemical compound C12=CC=C(N)C=C2C(C)(C)CC1(C)C1=CC=C(N)C=C1 CGSKOGYKWHUSLC-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- RPOHXHHHVSGUMN-UHFFFAOYSA-N 1-n,4-n-bis(4-aminophenyl)benzene-1,4-dicarboxamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=C(C(=O)NC=2C=CC(N)=CC=2)C=C1 RPOHXHHHVSGUMN-UHFFFAOYSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 1
- YJLVXRPNNDKMMO-UHFFFAOYSA-N 3,4,5,6-tetrafluorophthalic acid Chemical compound OC(=O)C1=C(F)C(F)=C(F)C(F)=C1C(O)=O YJLVXRPNNDKMMO-UHFFFAOYSA-N 0.000 description 1
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 1
- GWHLJVMSZRKEAQ-UHFFFAOYSA-N 3-(2,3-dicarboxyphenyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O GWHLJVMSZRKEAQ-UHFFFAOYSA-N 0.000 description 1
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 1
- LJMPOXUWPWEILS-UHFFFAOYSA-N 3a,4,4a,7a,8,8a-hexahydrofuro[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1C2C(=O)OC(=O)C2CC2C(=O)OC(=O)C21 LJMPOXUWPWEILS-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 description 1
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical compound CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 1
- OSUWBBMPVXVSOA-UHFFFAOYSA-N 4-(4-carbonochloridoylphenoxy)benzoyl chloride Chemical compound C1=CC(C(=O)Cl)=CC=C1OC1=CC=C(C(Cl)=O)C=C1 OSUWBBMPVXVSOA-UHFFFAOYSA-N 0.000 description 1
- QDBOAKPEXMMQFO-UHFFFAOYSA-N 4-(4-carbonochloridoylphenyl)benzoyl chloride Chemical compound C1=CC(C(=O)Cl)=CC=C1C1=CC=C(C(Cl)=O)C=C1 QDBOAKPEXMMQFO-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- RBCRDGPAIUTPGK-UHFFFAOYSA-N 4-[1-(4-aminophenyl)-9h-fluoren-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C1=CC=C(C=2C(=CC=CC=2)C2)C2=C1C1=CC=C(N)C=C1 RBCRDGPAIUTPGK-UHFFFAOYSA-N 0.000 description 1
- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 description 1
- HHLMWQDRYZAENA-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 HHLMWQDRYZAENA-UHFFFAOYSA-N 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 1
- NKYXYJFTTIPZDE-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenoxy]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1OC1=CC=C(N)C=C1C(F)(F)F NKYXYJFTTIPZDE-UHFFFAOYSA-N 0.000 description 1
- OSFGNTLIOUHOKN-UHFFFAOYSA-N 4-[benzyl(methyl)sulfamoyl]benzoic acid Chemical compound C=1C=C(C(O)=O)C=CC=1S(=O)(=O)N(C)CC1=CC=CC=C1 OSFGNTLIOUHOKN-UHFFFAOYSA-N 0.000 description 1
- XPAQFJJCWGSXGJ-UHFFFAOYSA-N 4-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=C(N)C=C1 XPAQFJJCWGSXGJ-UHFFFAOYSA-N 0.000 description 1
- DVIPPHSQIBKWSA-UHFFFAOYSA-N 4-chlorophthalic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1C(O)=O DVIPPHSQIBKWSA-UHFFFAOYSA-N 0.000 description 1
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 1
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 description 1
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 1
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- 239000004805 Cyclohexane-1,2-dicarboxylic acid Substances 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003660 carbonate based solvent Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- ILUAAIDVFMVTAU-UHFFFAOYSA-N cyclohex-4-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CC=CCC1C(O)=O ILUAAIDVFMVTAU-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- STZIXLPVKZUAMV-UHFFFAOYSA-N cyclopentane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1(C(O)=O)C(O)=O STZIXLPVKZUAMV-UHFFFAOYSA-N 0.000 description 1
- ASJCSAKCMTWGAH-UHFFFAOYSA-N cyclopentane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCC1C(O)=O ASJCSAKCMTWGAH-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000001641 gel filtration chromatography Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/14—Polyamide-imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Description
本発明はポリアミド－イミド樹脂、ポリアミド－イミドワニス及びポリアミド－イミドフィルムに関する。 The present invention relates to polyamide-imide resins, polyamide-imide varnishes and polyamide-imide films.
一般に、ポリイミド樹脂は優れた機械的特性及び耐熱性を有することから、電気・電子部品等の分野において様々な利用が検討されている。例えば、液晶ディスプレイやＯＬＥＤディスプレイ等の画像表示装置に用いられるガラス基板を、デバイスの軽量化やフレキシブル化を目的として、プラスチック基板へ代替することが望まれており、当該プラスチック基板として適するポリイミドフィルムの研究が進められている。このような用途のポリイミドフィルムには高い透明性が求められる。 In general, since polyimide resins have excellent mechanical properties and heat resistance, various uses are being considered in the fields of electrical and electronic components. For example, it is desired to replace the glass substrates used in image display devices such as liquid crystal displays and OLED displays with plastic substrates in order to make the devices lighter and more flexible. Research is underway. Polyimide films for such uses are required to have high transparency.
ガラス支持体やシリコンウェハ上に塗布したワニスを加熱してポリイミドフィルムを形成すると、ポリイミドフィルムに残留応力が生じる。ポリイミドフィルムの残留応力が大きいと、ガラス支持体やシリコンウェハが反ってしまうという問題が生じるため、ポリイミドフィルムには残留応力の低減も求められる。
一方、ポリイミドフィルムの主材料であるポリイミド樹脂にポリアミドを混合または共重合しようとする試みが行われている。
特許文献１には、熱的、機械的および光学的特性に優れる共重合ポリアミド－イミドフィルムとして、２，２’－ビス（トリフルオロメチル）ベンジジンに由来する単位構造、４，４’－（ヘキサフルオロイソプロピリデン）ジフタル酸無水物に由来する単位構造、３，３’，４，４’－ビフェニルテトラカルボン二酸無水物に由来する単位構造およびテレフタル酸クロリド（ＴＰＣ）に由来する単位構造を有する樹脂が開示されている。
特許文献２には、４，４’－（ヘキサフルオロイソプロピリデン）ジフタル酸無水物と、シクロブタンテトラカルボン酸二無水物、及びシクロペンタンテトラカルボン酸二無水物から選択される１種以上を含む芳香族ジアンヒドリドと、芳香族ジカルボニル化合物と、２，２’－ビス（トリフルオロメチル）ベンジジンを含む芳香族ジアミンと、が共重合されたポリアミック酸のイミド化物である、ポリアミド－イミド樹脂が開示されている。When a polyimide film is formed by heating a varnish coated on a glass support or a silicon wafer, residual stress is generated in the polyimide film. If the residual stress of a polyimide film is large, there will be a problem that the glass support or silicon wafer will warp, so polyimide films are also required to have reduced residual stress.
On the other hand, attempts have been made to mix or copolymerize polyamide with polyimide resin, which is the main material of polyimide films.
Patent Document 1 describes a unit structure derived from 2,2'-bis(trifluoromethyl)benzidine, 4,4'-(hexane) as a copolyamide-imide film with excellent thermal, mechanical, and optical properties. It has a unit structure derived from diphthalic anhydride (fluoroisopropylidene), a unit structure derived from 3,3',4,4'-biphenyltetracarboxylic anhydride, and a unit structure derived from terephthalic acid chloride (TPC). A resin is disclosed.
Patent Document 2 describes a fragrance containing one or more selected from 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, cyclobutanetetracarboxylic dianhydride, and cyclopentanetetracarboxylic dianhydride. A polyamide-imide resin is disclosed, which is an imidized product of polyamic acid in which a group dianhydride, an aromatic dicarbonyl compound, and an aromatic diamine containing 2,2'-bis(trifluoromethyl)benzidine are copolymerized. has been done.
上述のように、ポリイミドフィルムには高透明性や低残留応力が要求されるが、優れた機械的特性及び耐熱性を維持しながら、それら特性を向上させることは容易ではない。
本発明はこのような状況に鑑みてなされたものであり、本発明の課題は、機械的特性、耐熱性、及び透明性に優れ、更に残留応力の低減が達成されるフィルムの形成が可能なポリアミド－イミド樹脂、並びに該ポリアミド－イミド樹脂を含むポリアミド－イミドワニス及びポリアミド－イミドフィルムを提供することにある。As mentioned above, polyimide films are required to have high transparency and low residual stress, but it is not easy to improve these properties while maintaining excellent mechanical properties and heat resistance.
The present invention was made in view of these circumstances, and an object of the present invention is to form a film that has excellent mechanical properties, heat resistance, and transparency, and further reduces residual stress. An object of the present invention is to provide a polyamide-imide resin, and a polyamide-imide varnish and polyamide-imide film containing the polyamide-imide resin.
本発明者らは、特定の構成単位の組み合わせを含むポリアミド－イミド樹脂が上記課題を解決できることを見出し、発明を完成させるに至った。 The present inventors have discovered that a polyamide-imide resin containing a combination of specific structural units can solve the above problems, and have completed the invention.
即ち、本発明は、下記の［１］～［８］に関する。
［１］
テトラカルボン酸二無水物に由来する構成単位Ａ、ジアミンに由来する構成単位Ｂ、及び芳香族ジカルボン酸クロリドに由来する構成単位Ｃを有するポリアミド－イミド樹脂であって、
構成単位Ａが下記式（ａ－１）で表される化合物に由来する構成単位（Ａ－１）を含み、
構成単位Ｂが下記式（ｂ－１）で表される化合物に由来する構成単位（Ｂ－１）を含み、
構成単位Ｃが下記式（ｃ－１）で表される化合物に由来する構成単位（Ｃ－１）を含む、ポリアミド－イミド樹脂。
[1]
A polyamide-imide resin having a structural unit A derived from a tetracarboxylic dianhydride, a structural unit B derived from a diamine, and a structural unit C derived from an aromatic dicarboxylic acid chloride,
The structural unit A contains a structural unit (A-1) derived from a compound represented by the following formula (a-1),
Structural unit B includes a structural unit (B-1) derived from a compound represented by the following formula (b-1),
A polyamide-imide resin containing a structural unit (C-1) in which the structural unit C is derived from a compound represented by the following formula (c-1).
［２］
構成単位Ａ及び構成単位Ｃの合計中における構成単位（Ａ－１）の比率が１０～９０モル％であり、
構構成単位Ａ及び構成単位Ｃの合計中における構成単位（Ｃ－１）の比率が１０～６０モル％である、上記［１］に記載のポリアミド－イミド樹脂。
［３］
構成単位Ａが下記式（ａ－２）で表される化合物に由来する構成単位（Ａ－２）を含む、請求項１又は２に記載のポリアミド－イミド樹脂。
［４］
構成単位Ａ及び構成単位Ｃの合計中における構成単位（Ａ－２）の比率が５０モル％以下である、上記［３］に記載のポリアミド－イミド樹脂。
［５］
構成単位Ｃ中における構成単位（Ｃ－１）の比率が５０モル％以上である、上記［１］～［４］のいずれかに記載のポリアミド－イミド樹脂。
［６］
構成単位Ｂ中における構成単位（Ｂ－１）の比率が５０モル％以上である、上記［１］～［５］のいずれかに記載のポリアミド－イミド樹脂。
［７］
上記［１］～［６］のいずれかに記載のポリアミド－イミド樹脂が有機溶媒に溶解してなるポリアミド－イミドワニス。
［８］
上記［１］～［６］のいずれかに記載のポリアミド－イミド樹脂を含む、ポリアミド－イミドフィルム。[2]
The ratio of the structural unit (A-1) in the total of the structural units A and C is 10 to 90 mol%,
The polyamide-imide resin according to [1] above, wherein the ratio of the structural unit (C-1) in the total of the structural unit A and the structural unit C is 10 to 60 mol%.
[3]
The polyamide-imide resin according to claim 1 or 2, wherein the structural unit A contains a structural unit (A-2) derived from a compound represented by the following formula (a-2).
[4]
The polyamide-imide resin according to [3] above, wherein the ratio of the structural unit (A-2) in the total of the structural units A and C is 50 mol% or less.
[5]
The polyamide-imide resin according to any one of [1] to [4] above, wherein the ratio of the structural unit (C-1) in the structural unit C is 50 mol% or more.
[6]
The polyamide-imide resin according to any one of [1] to [5] above, wherein the ratio of the structural unit (B-1) in the structural unit B is 50 mol% or more.
[7]
A polyamide-imide varnish obtained by dissolving the polyamide-imide resin according to any one of [1] to [6] above in an organic solvent.
[8]
A polyamide-imide film comprising the polyamide-imide resin according to any one of [1] to [6] above.
本発明によれば、機械的特性、耐熱性、及び透明性に優れ、更に残留応力の低減が達成されるフィルムを形成することができる。 According to the present invention, it is possible to form a film that is excellent in mechanical properties, heat resistance, and transparency, and further achieves reduction in residual stress.
［ポリアミド－イミド樹脂］
本発明のポリアミド－イミド樹脂は、テトラカルボン酸二無水物に由来する構成単位Ａ、ジアミンに由来する構成単位Ｂ、及び芳香族ジカルボン酸クロリドに由来する構成単位Ｃを有し、
構成単位Ａが下記式（ａ－１）で表される化合物に由来する構成単位（Ａ－１）を含み、
構成単位Ｂが下記式（ｂ－１）で表される化合物に由来する構成単位（Ｂ－１）を含み、
構成単位Ｃが下記式（ｃ－１）で表される化合物に由来する構成単位（Ｃ－１）を含む。
The polyamide-imide resin of the present invention has a structural unit A derived from a tetracarboxylic dianhydride, a structural unit B derived from a diamine, and a structural unit C derived from an aromatic dicarboxylic acid chloride,
The structural unit A contains a structural unit (A-1) derived from a compound represented by the following formula (a-1),
Structural unit B includes a structural unit (B-1) derived from a compound represented by the following formula (b-1),
The structural unit C includes a structural unit (C-1) derived from a compound represented by the following formula (c-1).
本発明のポリアミド－イミド樹脂は、その分子鎖中に構成単位Ａと構成単位Ｂとがイミド結合で連結してなる構造と、構成単位Ｃと構成単位Ｂとがアミド結合で連結してなる構造とを含むものである。 The polyamide-imide resin of the present invention has a structure in which a structural unit A and a structural unit B are connected by an imide bond in its molecular chain, and a structure in which a structural unit C and a structural unit B are connected by an amide bond. This includes:
＜構成単位Ａ＞
構成単位Ａは、ポリアミド－イミド樹脂に占めるテトラカルボン酸二無水物に由来する構成単位であって、下記式（ａ－１）で表される化合物に由来する構成単位（Ａ－１）を含む。構成単位Ａは、構成単位（Ａ－１）の他に、下記式（ａ－２）で表される化合物に由来する構成単位（Ａ－２）を含んでいてもよい。
Structural unit A is a structural unit derived from tetracarboxylic dianhydride that occupies the polyamide-imide resin, and includes a structural unit (A-1) derived from a compound represented by the following formula (a-1). . In addition to the structural unit (A-1), the structural unit A may include a structural unit (A-2) derived from a compound represented by the following formula (a-2).
式（ａ－１）で表される化合物は、ノルボルナン－２－スピロ－α－シクロペンタノン－α’－スピロ－２’’－ノルボルナン－５，５’’，６，６’’－テトラカルボン酸二無水物である。 The compound represented by formula (a-1) is norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic It is an acid dianhydride.
式（ａ－２）で表される化合物は、ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）であり、その具体例としては、下記式（ａ－２ｓ）で表される３，３’，４，４’－ビフェニルテトラカルボン酸二無水物（ｓ－ＢＰＤＡ）、下記式（ａ－２ａ）で表される２，３，３’，４’－ビフェニルテトラカルボン酸二無水物（ａ－ＢＰＤＡ）、下記式（ａ－２ｉ）で表される２，２’，３，３’－ビフェニルテトラカルボン酸二無水物（ｉ－ＢＰＤＡ）が挙げられる。
構成単位Ａが構成単位（Ａ－１）を少なくとも含むことによって、フィルムの機械的特性、耐熱性及び透明性がより向上し、残留応力がより低下する。また、構成単位Ａが構成単位（Ａ－１）の他に、構成単位（Ａ－２）を含むことによって、フィルムの機械的特性がより一層向上し、残留応力がより一層低下する。 When the structural unit A contains at least the structural unit (A-1), the mechanical properties, heat resistance, and transparency of the film are further improved, and the residual stress is further reduced. Further, when the structural unit A includes the structural unit (A-2) in addition to the structural unit (A-1), the mechanical properties of the film are further improved and the residual stress is further reduced.
構成単位Ａ中における構成単位（Ａ－１）の比率は、好ましくは３０モル％以上であり、より好ましくは４０モル％以上であり、更に好ましくは５０モル％以上である。当該構成単位（Ａ－１）の比率の上限値は特に限定されず、即ち、１００モル％である。構成単位Ａは構成単位（Ａ－１）のみからなっていてもよい。 The ratio of the structural unit (A-1) in the structural unit A is preferably 30 mol% or more, more preferably 40 mol% or more, and even more preferably 50 mol% or more. The upper limit of the ratio of the structural unit (A-1) is not particularly limited, that is, 100 mol%. The structural unit A may consist only of the structural unit (A-1).
構成単位Ａ中における構成単位（Ａ－２）の比率は、好ましくは７０モル％以下であり、より好ましくは１５～６０モル％であり、更に好ましくは２５～５０モル％である。
構成単位Ａ中における構成単位（Ａ－１）及び（Ａ－２）の合計の比率は、好ましくは５０モル％以上であり、より好ましくは７０モル％以上であり、更に好ましくは９０モル％以上であり、特に好ましくは９９モル％以上である。構成単位（Ａ－１）及び（Ａ－２）の合計の比率の上限値は特に限定されず、即ち、１００モル％である。構成単位Ａは構成単位（Ａ－１）及び構成単位（Ａ－２）のみからなっていてもよい。The ratio of the structural unit (A-2) in the structural unit A is preferably 70 mol% or less, more preferably 15 to 60 mol%, and still more preferably 25 to 50 mol%.
The total ratio of structural units (A-1) and (A-2) in structural unit A is preferably 50 mol% or more, more preferably 70 mol% or more, and even more preferably 90 mol% or more. and particularly preferably 99 mol% or more. The upper limit of the total ratio of structural units (A-1) and (A-2) is not particularly limited, that is, 100 mol%. The structural unit A may consist only of the structural unit (A-1) and the structural unit (A-2).
構成単位Ａ及び構成単位Ｃの合計中における構成単位（Ａ－１）の比率は、好ましくは１０～９０モル％であり、より好ましくは３０～８５モル％であり、更に好ましくは３５～７５モル％である。
構成単位Ａ及び構成単位Ｃの合計中における構成単位（Ａ－２）の比率は、好ましくは５０モル％以下であり、より好ましくは５～４５モル％であり、更に好ましくは１０～３５モル％である。
構成単位Ａ及び構成単位Ｃの合計中における構成単位（Ａ－１）及び（Ａ－２）の合計の比率は、好ましくは４０～９０モル％であり、より好ましくは５０～８５モル％であり、更に好ましくは６０～７５モル％である。The ratio of the structural unit (A-1) in the total of the structural unit A and the structural unit C is preferably 10 to 90 mol%, more preferably 30 to 85 mol%, and even more preferably 35 to 75 mol%. %.
The ratio of the structural unit (A-2) in the total of structural units A and C is preferably 50 mol% or less, more preferably 5 to 45 mol%, and even more preferably 10 to 35 mol%. It is.
The ratio of the total of structural units (A-1) and (A-2) in the total of structural units A and C is preferably 40 to 90 mol%, more preferably 50 to 85 mol%. , more preferably 60 to 75 mol%.
構成単位Ａは、構成単位（Ａ－１）及び（Ａ－２）以外の構成単位を含んでもよい。そのような構成単位を与えるテトラカルボン酸二無水物としては、特に限定されないが、ピロメリット酸二無水物、９，９’－ビス（３，４－ジカルボキシフェニル）フルオレン二無水物、及び４，４’－(ヘキサフルオロイソプロピリデン)ジフタル酸無水物等の芳香族テトラカルボン酸二無水物（ただし、式（ａ－２）で表される化合物を除く）；１，２，３，４－シクロブタンテトラカルボン酸二無水物、及び１，２，４，５－シクロヘキサンテトラカルボン酸二無水物等の脂環式テトラカルボン酸二無水物（ただし、式（ａ－１）で表される化合物を除く）；並びに１，２，３，４－ブタンテトラカルボン酸二無水物等の脂肪族テトラカルボン酸二無水物が挙げられる。
なお、本明細書において、芳香族テトラカルボン酸二無水物とは芳香環を１つ以上含むテトラカルボン酸二無水物を意味し、脂環式テトラカルボン酸二無水物とは脂環を１つ以上含み、かつ芳香環を含まないテトラカルボン酸二無水物を意味し、脂肪族テトラカルボン酸二無水物とは芳香環も脂環も含まないテトラカルボン酸二無水物を意味する。
構成単位Ａに任意に含まれる構成単位（Ａ－１）及び（Ａ－２）以外の構成単位は、１種でもよいし、２種以上であってもよい。The structural unit A may include structural units other than the structural units (A-1) and (A-2). Tetracarboxylic dianhydrides providing such structural units include, but are not particularly limited to, pyromellitic dianhydride, 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride, and , 4'-(hexafluoroisopropylidene) diphthalic anhydride and other aromatic tetracarboxylic dianhydrides (excluding compounds represented by formula (a-2)); 1,2,3,4- Alicyclic tetracarboxylic dianhydrides such as cyclobutanetetracarboxylic dianhydride and 1,2,4,5-cyclohexanetetracarboxylic dianhydride (however, compounds represented by formula (a-1) ); and aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride.
In addition, in this specification, aromatic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing one or more aromatic rings, and alicyclic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing one or more alicyclic rings. The term "aliphatic tetracarboxylic dianhydride" refers to a tetracarboxylic dianhydride containing the above and not containing an aromatic ring, and the term "aliphatic tetracarboxylic dianhydride" refers to a tetracarboxylic dianhydride containing neither an aromatic ring nor an alicyclic ring.
The number of structural units other than the structural units (A-1) and (A-2) optionally included in the structural unit A may be one or two or more types.
＜構成単位Ｂ＞
構成単位Ｂは、ポリアミド－イミド樹脂に占めるジアミンに由来する構成単位であって、下記式（ｂ－１）で表される化合物に由来する構成単位（Ｂ－１）を含む。
Structural unit B is a structural unit derived from a diamine that occupies the polyamide-imide resin, and includes a structural unit (B-1) derived from a compound represented by the following formula (b-1).
式（ｂ－１）で表される化合物は、２，２’－ビス（トリフルオロメチル）ベンジジンである。
構成単位Ｂが構成単位（Ｂ－１）を含むことによって、フィルムの透明性及び耐熱性が向上し、残留応力が低下する。The compound represented by formula (b-1) is 2,2'-bis(trifluoromethyl)benzidine.
When the structural unit B contains the structural unit (B-1), the transparency and heat resistance of the film are improved, and the residual stress is reduced.
構成単位Ｂ中における構成単位（Ｂ－１）の比率は、好ましくは５０モル％以上であり、より好ましくは７０モル％以上であり、更に好ましくは９０モル％以上であり、特に好ましくは９９モル％以上である。構成単位（Ｂ－１）の比率の上限値は特に限定されず、即ち、１００モル％である。構成単位Ｂは構成単位（Ｂ－１）のみからなっていてもよい。 The ratio of the structural unit (B-1) in the structural unit B is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99 mol%. % or more. The upper limit of the ratio of the structural unit (B-1) is not particularly limited, that is, 100 mol%. The structural unit B may consist only of the structural unit (B-1).
構成単位Ｂは構成単位（Ｂ－１）以外の構成単位を含んでもよい。そのような構成単位を与えるジアミンとしては、特に限定されないが、１，４－フェニレンジアミン、ｐ－キシリレンジアミン、３，５－ジアミノ安息香酸、１，５－ジアミノナフタレン、２，２’－ジメチルビフェニル－４，４’－ジアミン、４，４’－ジアミノジフェニルエーテル、４，４’－ジアミノジフェニルメタン、２，２－ビス（４－アミノフェニル）ヘキサフルオロプロパン、４，４’－ジアミノジフェニルスルホン、４，４’－ジアミノベンズアニリド、１－(４－アミノフェニル)－２，３－ジヒドロ－１，３，３－トリメチル－１Ｈ－インデン－５－アミン、α，α’－ビス（４－アミノフェニル）－１，４－ジイソプロピルベンゼン、Ｎ，Ｎ’－ビス（４－アミノフェニル）テレフタルアミド、４，４’－ビス（４－アミノフェノキシ）ビフェニル、２，２－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパン、２，２－ビス（４－（４－アミノフェノキシ）フェニル）ヘキサフルオロプロパン、２，２’－ビス（トリフルオロメチル）－４，４’－ジアミノジフェニルエーテル、及び９，９－ビス（４－アミノフェニル）フルオレン等の芳香族ジアミン（ただし、式（ｂ－１）で表される化合物を除く）；１，３－ビス（アミノメチル）シクロヘキサン、及び１，４－ビス（アミノメチル）シクロヘキサン等の脂環式ジアミン；並びにエチレンジアミン及びヘキサメチレンジアミン等の脂肪族ジアミンが挙げられる。
なお、本明細書において、芳香族ジアミンとは芳香環を１つ以上含むジアミンを意味し、脂環式ジアミンとは脂環を１つ以上含み、かつ芳香環を含まないジアミンを意味し、脂肪族ジアミンとは芳香環も脂環も含まないジアミンを意味する。
構成単位Ｂに任意に含まれる構成単位（Ｂ－１）以外の構成単位は、１種でもよいし、２種以上であってもよい。The structural unit B may include structural units other than the structural unit (B-1). Diamines that provide such structural units include, but are not particularly limited to, 1,4-phenylenediamine, p-xylylenediamine, 3,5-diaminobenzoic acid, 1,5-diaminonaphthalene, 2,2'-dimethyl Biphenyl-4,4'-diamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-diaminodiphenyl sulfone, 4 , 4'-diaminobenzanilide, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine, α,α'-bis(4-aminophenyl) )-1,4-diisopropylbenzene, N,N'-bis(4-aminophenyl)terephthalamide, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-amino phenoxy)phenyl]propane, 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane, 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether, and 9,9 - Aromatic diamines such as bis(4-aminophenyl)fluorene (excluding compounds represented by formula (b-1)); 1,3-bis(aminomethyl)cyclohexane, and 1,4-bis( and aliphatic diamines such as ethylene diamine and hexamethylene diamine.
In addition, in this specification, aromatic diamine means a diamine containing one or more aromatic rings, alicyclic diamine means a diamine containing one or more alicyclic rings and no aromatic ring, Group diamine means a diamine containing neither aromatic ring nor alicyclic ring.
The number of structural units other than the structural unit (B-1) optionally included in the structural unit B may be one type or two or more types.
＜構成単位Ｃ＞
構成単位Ｃは、ポリアミド－イミド樹脂に占める芳香族ジカルボン酸クロリドに由来する構成単位であって、下記式（ｃ－１）で表される化合物に由来する構成単位（Ｃ－１）を含む。
The structural unit C is a structural unit derived from an aromatic dicarboxylic acid chloride that occupies the polyamide-imide resin, and includes a structural unit (C-1) derived from a compound represented by the following formula (c-1).
式（ｃ－１）で表される化合物は、テレフタル酸クロリドである。
構成単位Ｃが構成単位（Ｃ－１）を含むことによって、フィルムの機械的特性、耐熱性及び透明性が向上し、残留応力が低下する。The compound represented by formula (c-1) is terephthalic acid chloride.
When the structural unit C contains the structural unit (C-1), the mechanical properties, heat resistance and transparency of the film are improved, and residual stress is reduced.
構成単位Ｃ中における構成単位（Ｃ－１）の比率は、好ましくは５０モル％以上であり、より好ましくは７０モル％以上であり、更に好ましくは９０モル％以上であり、特に好ましくは９９モル％以上である。構成単位（Ｃ－１）の比率の上限値は特に限定されず、即ち、１００モル％である。構成単位Ｃは構成単位（Ｃ－１）のみからなっていてもよい。
構成単位Ａ及び構成単位Ｃの合計中における構成単位（Ｃ－１）の比率は、好ましくは１０～６０モル％であり、より好ましくは１５～５０モル％であり、更に好ましくは２５～４０モル％である。The ratio of the structural unit (C-1) in the structural unit C is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99 mol%. % or more. The upper limit of the ratio of the structural unit (C-1) is not particularly limited, ie, 100 mol%. The structural unit C may consist only of the structural unit (C-1).
The ratio of the structural unit (C-1) in the total of the structural unit A and the structural unit C is preferably 10 to 60 mol%, more preferably 15 to 50 mol%, and still more preferably 25 to 40 mol%. %.
構成単位Ｃは、構成単位（Ｃ－１）以外の構成単位を含んでもよい。そのような構成単位を与える芳香族ジカルボン酸クロリドとしては、特に限定されないが、４，４’－ビフェニルジカルボニルクロリド、４，４’－オキシジベンゾイルクロリド、イソフタル酸クロリド等が挙げられる。
構成単位Ｃに任意に含まれる構成単位（Ｃ－１）以外の構成単位は、１種でもよいし、２種以上であってもよい。The structural unit C may include structural units other than the structural unit (C-1). Aromatic dicarboxylic acid chlorides that provide such structural units include, but are not particularly limited to, 4,4'-biphenyldicarbonyl chloride, 4,4'-oxydibenzoyl chloride, isophthalic acid chloride, and the like.
The number of structural units other than the structural unit (C-1) optionally included in the structural unit C may be one type or two or more types.
本発明のポリアミド－イミド樹脂の数平均分子量は、得られるポリアミド－イミドフィルムの機械的強度の観点から、好ましくは５，０００～３００，０００、より好ましくは５，０００～１００，０００である。なお、ポリアミド－イミド樹脂の数平均分子量は、例えば、ゲルろ過クロマトグラフィー測定による標準ポリメチルメタクリレート（ＰＭＭＡ）換算値より求めることができる。 The number average molecular weight of the polyamide-imide resin of the present invention is preferably 5,000 to 300,000, more preferably 5,000 to 100,000, from the viewpoint of mechanical strength of the polyamide-imide film obtained. The number average molecular weight of the polyamide-imide resin can be determined, for example, from a standard polymethyl methacrylate (PMMA) value measured by gel filtration chromatography.
本発明のポリアミド－イミド樹脂は、ポリイミド鎖（構成単位Ａと構成単位Ｂとがイミド結合してなる構造）と、ポリアミド鎖（構成単位Ｃと構成単位Ｂとがアミド結合してなる構造）とを含む構造等が挙げられる。
本発明のポリアミド－イミド樹脂中における、構成単位Ａと構成単位Ｃのモル比率（構成単位Ａ／構成単位Ｃ）は、好ましくは４０／６０～９０／１０、より好ましくは５０／５０～８５／１５、更に好ましくは６０／４０～７５／２５である。The polyamide-imide resin of the present invention has a polyimide chain (a structure formed by an imide bond between a structural unit A and a structural unit B) and a polyamide chain (a structure formed by an amide bond between a structural unit C and a structural unit B). Examples include structures that include.
The molar ratio of structural unit A to structural unit C (constituent unit A/constituent unit C) in the polyamide-imide resin of the present invention is preferably 40/60 to 90/10, more preferably 50/50 to 85/1. 15, more preferably 60/40 to 75/25.
本発明のポリアミド－イミド樹脂は、ポリイミド鎖（構成単位Ａと構成単位Ｂとがイミド結合してなる構造）と、ポリアミド鎖（構成単位Ｃと構成単位Ｂとがアミド結合してなる構造）を主たる構造として含むことが好ましい。したがって、本発明ポリアミド－イミド樹脂中に占めるポリイミド鎖及びポリアミド鎖の合計の比率は、好ましくは３０質量％以上であり、より好ましくは４０質量％以上であり、更に好ましくは５０質量％以上であり、特に好ましくは６０質量％以上である。 The polyamide-imide resin of the present invention has a polyimide chain (a structure formed by an imide bond between a structural unit A and a structural unit B) and a polyamide chain (a structure formed by an amide bond between a structural unit C and a structural unit B). It is preferable to include it as the main structure. Therefore, the total proportion of polyimide chains and polyamide chains in the polyamide-imide resin of the present invention is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more. , particularly preferably 60% by mass or more.
本発明のポリアミド－イミド樹脂を用いることで、機械的特性、耐熱性、及び透明性に優れ、更に残留応力の低減が達成されるフィルムを形成することができ、当該フィルムの有する好適な物性値は以下の通りである。 By using the polyamide-imide resin of the present invention, it is possible to form a film that has excellent mechanical properties, heat resistance, and transparency, and further reduces residual stress, and the film has suitable physical property values. is as follows.
引張弾性率は、好ましくは２．５ＧＰａ以上であり、より好ましくは３．０ＧＰａ以上であり、更に好ましくは４．０ＧＰａ以上である。
引張強度は、好ましくは１００ＭＰａ以上であり、より好ましくは１２０ＭＰａ以上であり、更に好ましくは１５０ＭＰａ以上である。
ガラス転移温度（Ｔｇ）は、好ましくは３２０℃以上であり、より好ましくは３５０℃以上であり、更に好ましくは３６５℃以上である。
全光線透過率は、厚さ１０μｍのフィルムとした際に、好ましくは８８％以上であり、より好ましくは８８．５％以上であり、更に好ましくは８９％以上である。
残留応力は、好ましくは１８．０ＭＰａ以下であり、より好ましくは１５．０ＭＰａ以下であり、更に好ましくは１０．０ＭＰａ以下である。
なお、本発明における上述の物性値は、具体的には実施例に記載の方法で測定することができる。The tensile modulus is preferably 2.5 GPa or more, more preferably 3.0 GPa or more, still more preferably 4.0 GPa or more.
The tensile strength is preferably 100 MPa or more, more preferably 120 MPa or more, still more preferably 150 MPa or more.
The glass transition temperature (Tg) is preferably 320°C or higher, more preferably 350°C or higher, and still more preferably 365°C or higher.
The total light transmittance is preferably 88% or more, more preferably 88.5% or more, and even more preferably 89% or more when the film has a thickness of 10 μm.
The residual stress is preferably 18.0 MPa or less, more preferably 15.0 MPa or less, still more preferably 10.0 MPa or less.
In addition, the above-mentioned physical property values in the present invention can be specifically measured by the method described in the Examples.
［ポリアミド－イミド樹脂の製造方法］
本発明のポリアミド－イミド樹脂は、上述の構成単位（Ａ－１）を与える化合物を含むテトラカルボン酸成分と、上述の構成単位（Ｂ－１）を与える化合物を含むジアミン成分とを反応させた後に、構成単位（Ｃ－１）を与える化合物を含むジカルボン酸成分を反応させることにより製造することができる。[Production method of polyamide-imide resin]
The polyamide-imide resin of the present invention is obtained by reacting a tetracarboxylic acid component containing a compound that provides the above-mentioned structural unit (A-1) with a diamine component that contains a compound that provides the above-mentioned structural unit (B-1). It can be produced by subsequently reacting a dicarboxylic acid component containing a compound that provides the structural unit (C-1).
構成単位（Ａ－１）を与える化合物としては、式（ａ－１）で表される化合物が挙げられるが、それに限られず、同じ構成単位を与える範囲でその誘導体であってもよい。当該誘導体としては、式（ａ－１）で表されるテトラカルボン酸二無水物に対応するテトラカルボン酸（即ち、ノルボルナン－２－スピロ－α－シクロペンタノン－α’－スピロ－２’’－ノルボルナン－５，５’’，６，６’’－テトラカルボン酸）、及び当該テトラカルボン酸のアルキルエステルが挙げられる。構成単位（Ａ－１）を与える化合物としては、式（ａ－１）で表される化合物（即ち、二無水物）が好ましい。 Examples of the compound that provides the structural unit (A-1) include the compound represented by formula (a-1), but the compound is not limited thereto, and derivatives thereof may be used as long as they provide the same structural unit. The derivative includes a tetracarboxylic acid corresponding to the tetracarboxylic dianhydride represented by formula (a-1) (i.e., norbornane-2-spiro-α-cyclopentanone-α'-spiro-2'' -norbornane-5,5'',6,6''-tetracarboxylic acid) and alkyl esters of the tetracarboxylic acid. As the compound providing structural unit (A-1), a compound represented by formula (a-1) (ie, dianhydride) is preferable.
テトラカルボン酸成分は、上述の構成単位（Ａ－２）を与える化合物を含んでいてもよい。
構成単位（Ａ－２）を与える化合物としては、式（ａ－２）で表される化合物が挙げられるが、それに限られず、同じ構成単位を与える範囲でその誘導体であってもよい。当該誘導体としては、式（ａ－２）で表されるテトラカルボン酸二無水物に対応するテトラカルボン酸及び当該テトラカルボン酸のアルキルエステルが挙げられる。構成単位（Ａ－２）を与える化合物としては、式（ａ－２）で表される化合物（即ち、二無水物）が好ましい。The tetracarboxylic acid component may contain a compound that provides the above-mentioned structural unit (A-2).
Examples of the compound that provides the structural unit (A-2) include the compound represented by formula (a-2), but the compound is not limited thereto, and derivatives thereof may be used as long as they provide the same structural unit. Examples of such derivatives include tetracarboxylic acids corresponding to the tetracarboxylic dianhydride represented by formula (a-2) and alkyl esters of the tetracarboxylic acids. As the compound providing structural unit (A-2), a compound represented by formula (a-2) (ie, dianhydride) is preferable.
テトラカルボン酸成分は、構成単位（Ａ－１）を与える化合物を、好ましくは３０モル％以上含み、より好ましくは４０モル％以上含み、更に好ましくは５０モル％以上含む。構成単位（Ａ－１）を与える化合物の含有量の上限値は特に限定されず、即ち、１００モル％である。テトラカルボン酸成分は構成単位（Ａ－１）を与える化合物のみからなっていてもよい。 The tetracarboxylic acid component preferably contains 30 mol% or more, more preferably 40 mol% or more, still more preferably 50 mol% or more of the compound that provides the structural unit (A-1). The upper limit of the content of the compound providing the structural unit (A-1) is not particularly limited, that is, it is 100 mol%. The tetracarboxylic acid component may consist only of the compound that provides the structural unit (A-1).
テトラカルボン酸成分が構成単位（Ａ－２）を含む場合には、テトラカルボン酸成分は、構成単位（Ａ－２）を与える化合物を、好ましくは７０モル％以下含み、より好ましくは１５～６０モル％含み、更に好ましくは２５～５０モル％含む。
テトラカルボン酸成分は、構成単位（Ａ－１）を与える化合物及び構成単位（Ａ－２）を与える化合物を合計で、好ましくは５０モル％以上含み、より好ましくは７０モル％以上含み、更に好ましくは９０モル％以上含み、特に好ましくは９９モル％以上含む。構成単位（Ａ－１）を与える化合物及び構成単位（Ａ－２）を与える化合物の合計の含有量の上限値は特に限定されず、即ち、１００モル％である。テトラカルボン酸成分は構成単位（Ａ－１）を与える化合物および構成単位（Ａ－２）を与える化合物のみからなっていてもよい。When the tetracarboxylic acid component contains the structural unit (A-2), the tetracarboxylic acid component preferably contains 70 mol% or less, more preferably 15 to 60 mol% of the compound that provides the structural unit (A-2). Contains mol%, more preferably 25 to 50 mol%.
The tetracarboxylic acid component preferably contains a total of 50 mol% or more, more preferably 70 mol% or more, and even more preferably contains 90 mol% or more, particularly preferably 99 mol% or more. The upper limit of the total content of the compound providing the structural unit (A-1) and the compound providing the structural unit (A-2) is not particularly limited, that is, 100 mol%. The tetracarboxylic acid component may consist only of a compound that provides the structural unit (A-1) and a compound that provides the structural unit (A-2).
テトラカルボン酸成分は、構成単位（Ａ－１）を与える化合物及び構成単位（Ａ－２）を与える化合物以外の化合物を含んでもよく、当該化合物としては、上述の芳香族テトラカルボン酸二無水物、脂環式テトラカルボン酸二無水物、及び脂肪族テトラカルボン酸二無水物、並びにそれらの誘導体（テトラカルボン酸、テトラカルボン酸のアルキルエステル等）が挙げられる。
テトラカルボン酸成分に任意に含まれる構成単位（Ａ－１）を与える化合物及び構成単位（Ａ－２）を与える化合物以外の化合物は、１種でもよいし、２種以上であってもよい。The tetracarboxylic acid component may contain compounds other than the compound that provides the structural unit (A-1) and the compound that provides the structural unit (A-2), such as the above-mentioned aromatic tetracarboxylic dianhydride. , alicyclic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, and derivatives thereof (tetracarboxylic acid, alkyl ester of tetracarboxylic acid, etc.).
The number of compounds other than the compound providing the structural unit (A-1) and the compound providing the structural unit (A-2) optionally contained in the tetracarboxylic acid component may be one or two or more.
構成単位（Ｂ－１）を与える化合物としては、式（ｂ－１）で表される化合物が挙げられるが、それに限られず、同じ構成単位を与える範囲でその誘導体であってもよい。当該誘導体としては、式（ｂ－１）で表されるジアミンに対応するジイソシアネートが挙げられる。構成単位（Ｂ－１）を与える化合物としては、式（ｂ－１）で表される化合物（即ち、ジアミン）が好ましい。 Examples of the compound that provides the structural unit (B-1) include the compound represented by formula (b-1), but the compound is not limited thereto, and derivatives thereof may be used as long as they provide the same structural unit. Examples of such derivatives include diisocyanates corresponding to the diamine represented by formula (b-1). As the compound providing the structural unit (B-1), a compound represented by formula (b-1) (ie, diamine) is preferable.
ジアミン成分は、構成単位（Ｂ－１）を与える化合物を、好ましくは５０モル％以上含み、より好ましくは７０モル％以上含み、更に好ましくは９０モル％以上含み、特に好ましくは９９モル％以上含む。構成単位（Ｂ－１）を与える化合物の含有量の上限値は特に限定されず、即ち、１００モル％である。ジアミン成分は構成単位（Ｂ－１）を与える化合物のみからなっていてもよい。 The diamine component preferably contains 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, particularly preferably 99 mol% or more of the compound that provides the structural unit (B-1). . The upper limit of the content of the compound providing the structural unit (B-1) is not particularly limited, that is, 100 mol%. The diamine component may consist only of the compound that provides the structural unit (B-1).
ジアミン成分は構成単位（Ｂ－１）を与える化合物以外の化合物を含んでもよく、当該化合物としては、上述の芳香族ジアミン、脂環式ジアミン、及び脂肪族ジアミン、並びにそれらの誘導体（ジイソシアネート等）が挙げられる。
ジアミン成分に任意に含まれる構成単位（Ｂ－１）を与える化合物以外の化合物は、１種でもよいし、２種以上であってもよい。The diamine component may contain a compound other than the compound providing the structural unit (B-1), and such compounds include the above-mentioned aromatic diamines, alicyclic diamines, aliphatic diamines, and derivatives thereof (diisocyanates, etc.) can be mentioned.
The number of compounds other than the compound providing the structural unit (B-1) optionally included in the diamine component may be one or two or more.
構成単位（Ｃ－１）を与える化合物としては、式（ｃ－１）で表される化合物が挙げられるが、それに限られず、同じ構成単位を与える範囲でその誘導体であってもよい。当該誘導体としては、式（ｃ－１）で表されるジカルボン酸クロリドに対応する他のジカルボン酸ハロゲン化物（即ち、酸フッ化物、酸臭化物、酸ヨウ化物）が挙げられる。構成単位（Ｃ－１）を与える化合物としては、式（ｃ－１）で表される化合物（即ち、酸塩化物）が好ましい。 Examples of the compound that provides the structural unit (C-1) include the compound represented by formula (c-1), but the compound is not limited thereto, and derivatives thereof may be used as long as they provide the same structural unit. Examples of such derivatives include other dicarboxylic acid halides (ie, acid fluorides, acid bromides, and acid iodides) corresponding to the dicarboxylic acid chloride represented by formula (c-1). As the compound providing the structural unit (C-1), a compound represented by formula (c-1) (ie, an acid chloride) is preferable.
ジカルボン酸成分は、構成単位（Ｃ－１）を与える化合物を、好ましくは５０モル％以上含み、より好ましくは７０モル％以上含み、更に好ましくは９０モル％以上含み、特に好ましくは９９モル％以上含む。構成単位（Ｃ－１）を与える化合物の含有量の上限値は特に限定されず、即ち、１００モル％である。ジカルボン酸成分は構成単位（Ｃ－１）を与える化合物のみからなっていてもよい。 The dicarboxylic acid component preferably contains a compound providing the structural unit (C-1) in an amount of 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, particularly preferably 99 mol% or more. include. The upper limit of the content of the compound providing the structural unit (C-1) is not particularly limited, that is, 100 mol%. The dicarboxylic acid component may consist only of the compound that provides the structural unit (C-1).
ジカルボン酸成分は構成単位（Ｃ－１）を与える化合物以外の化合物を含んでもよく、当該化合物としては、上述の芳香族ジカルボン酸クロリド、それらに対応する他のカルボン酸ハロゲン化物（即ち、酸フッ化物、酸臭化物、酸ヨウ化物）が挙げられる。
ジカルボン酸成分に任意に含まれる構成単位（Ｃ－１）を与える化合物以外の化合物は、１種でもよいし、２種以上であってもよい。The dicarboxylic acid component may contain a compound other than the compound providing the structural unit (C-1), and examples of such compounds include the above-mentioned aromatic dicarboxylic acid chlorides and other corresponding carboxylic acid halides (i.e., acid fluoride). compounds, acid bromides, acid iodides).
The number of compounds other than the compound providing the structural unit (C-1) optionally included in the dicarboxylic acid component may be one or two or more.
本発明において、ポリアミド－イミド樹脂の製造に用いるテトラカルボン酸成分及びジカルボン酸成分の合計とジアミン成分との仕込み量比〔（テトラカルボン酸成分＋ジカルボン酸成分）／ジアミン成分、モル比〕は、テトラカルボン酸成分及びジカルボン酸成分の合計１モルに対してジアミン成分が０．９～１．１モルであることが好ましい。 In the present invention, the charging amount ratio of the total of the tetracarboxylic acid component and dicarboxylic acid component and the diamine component used in the production of the polyamide-imide resin [(tetracarboxylic acid component + dicarboxylic acid component)/diamine component, molar ratio] is: The diamine component is preferably 0.9 to 1.1 mol per 1 mol of the tetracarboxylic acid component and the dicarboxylic acid component in total.
本発明において、ポリアミド－イミド樹脂の製造に用いるテトラカルボン酸成分とジカルボン酸成分との仕込み量比（テトラカルボン酸成分／ジカルボン酸成分、モル比）は、４０／６０～９０／１０が好ましく、５０／５０～８５／１５がより好ましく、６０／４０～７５／２５が更に好ましい。 In the present invention, the charging ratio of the tetracarboxylic acid component and the dicarboxylic acid component (tetracarboxylic acid component/dicarboxylic acid component, molar ratio) used for producing the polyamide-imide resin is preferably 40/60 to 90/10. More preferably 50/50 to 85/15, still more preferably 60/40 to 75/25.
また、本発明において、ポリアミド－イミド樹脂の製造には、前述のテトラカルボン酸成分ジカルボン酸成分、及びジアミン成分の他に、末端封止剤を用いてもよい。末端封止剤としてはモノアミン類あるいはジカルボン酸類が好ましい。
導入される末端封止剤の仕込み量としては、テトラカルボン酸成分１モルに対して０．０００１～０．１モルが好ましく、特に０．００１～０．０６モルが好ましい。
モノアミン類末端封止剤としては、例えば、メチルアミン、エチルアミン、プロピルアミン、ブチルアミン、ベンジルアミン、４－メチルベンジルアミン、４－エチルベンジルアミン、４－ドデシルベンジルアミン、３－メチルベンジルアミン、３－エチルベンジルアミン、アニリン、３－メチルアニリン、４－メチルアニリン等が推奨される。これらのうち、ベンジルアミン、アニリンが好適に使用できる。
ジカルボン酸類末端封止剤としては、ジカルボン酸類（但し、前述のジカルボン酸成分を除く）が挙げられ、分子内に有する２つのカルボキシ基が脱水縮合反応を起こした環状のカルボン酸無水物、及び当該カルボン酸無水物を形成しうるジカルボン酸が好ましい。具体的には、フタル酸、無水フタル酸、４－クロロフタル酸、テトラフルオロフタル酸、２，３－ベンゾフェノンジカルボン酸、３，４－ベンゾフェノンジカルボン酸、シクロヘキサン－１，２－ジカルボン酸、シクロペンタン－１，２－ジカルボン酸、４－シクロヘキセン－１，２－ジカルボン酸等が推奨される。これらのうち、フタル酸、無水フタル酸が好適に使用できる。Furthermore, in the present invention, in addition to the above-mentioned tetracarboxylic acid component, dicarboxylic acid component, and diamine component, a terminal capping agent may be used in the production of the polyamide-imide resin. As the terminal capping agent, monoamines or dicarboxylic acids are preferable.
The amount of the terminal capping agent to be introduced is preferably 0.0001 to 0.1 mol, particularly preferably 0.001 to 0.06 mol, per 1 mol of the tetracarboxylic acid component.
Examples of monoamine terminal capping agents include methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3-methylbenzylamine, 3- Ethylbenzylamine, aniline, 3-methylaniline, 4-methylaniline, etc. are recommended. Among these, benzylamine and aniline can be preferably used.
Examples of the dicarboxylic acid terminal capping agent include dicarboxylic acids (excluding the aforementioned dicarboxylic acid component), and cyclic carboxylic acid anhydrides in which two carboxyl groups in the molecule undergo a dehydration condensation reaction; Dicarboxylic acids capable of forming carboxylic anhydrides are preferred. Specifically, phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2,3-benzophenone dicarboxylic acid, 3,4-benzophenone dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid, cyclopentane- 1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, etc. are recommended. Among these, phthalic acid and phthalic anhydride can be preferably used.
前述のテトラカルボン酸成分とジアミン成分とジカルボン酸成分を反応させる方法には特に制限はなく、公知の方法を用いることができる。
具体的な反応方法としては、（１）テトラカルボン酸成分、ジアミン成分、及び反応溶剤を反応器に仕込み、室温～８０℃で０．５～３０時間撹拌し、その後に昇温してイミド化反応を行い、その後にジカルボン酸成分を加え、室温～８０℃で０．５～３０時間撹拌してアミド化反応を行う方法、（２）ジアミン成分及び反応溶剤を反応器に仕込んで溶解させた後、テトラカルボン酸成分を仕込み、必要に応じて室温～８０℃で０．５～３０時間撹拌し、その後に昇温してイミド化反応を行い、その後にジカルボン酸成分を加え、室温～８０℃で０．５～３０時間撹拌してアミド化反応を行う方法、（３）テトラカルボン酸成分、ジアミン成分、及び反応溶剤を反応器に仕込み、室温～８０℃で０．５～３０時間撹拌し、さらにジカルボン酸成分を加え、室温～８０℃で０．５～３０時間撹拌してアミド化反応を行い、その後に昇温してイミド化反応を行う方法、（４）ジアミン成分及び反応溶剤を反応器に仕込んで溶解させた後、テトラカルボン酸成分を仕込み、必要に応じて室温～８０℃で０．５～３０時間撹拌し、さらにジカルボン酸成分を加え、必要に応じて室温～８０℃で０．５～３０時間撹拌してアミド化反応を行い、その後に昇温してイミド化反応を行う方法、（５）テトラカルボン酸成分、ジアミン成分、ジカルボン酸成分、及び反応溶剤を反応器に仕込み、必要に応じて室温～８０℃で０．５～３０時間撹拌してアミド化反応を行い、その後に昇温してイミド化反応を行う方法等が挙げられる。There is no particular restriction on the method of reacting the above-mentioned tetracarboxylic acid component, diamine component, and dicarboxylic acid component, and any known method can be used.
The specific reaction method is as follows: (1) A tetracarboxylic acid component, a diamine component, and a reaction solvent are placed in a reactor, stirred at room temperature to 80°C for 0.5 to 30 hours, and then heated to imidize. A method of performing an amidation reaction by performing a reaction, then adding a dicarboxylic acid component, and stirring at room temperature to 80°C for 0.5 to 30 hours. (2) A method in which the diamine component and the reaction solvent were charged into a reactor and dissolved. After that, the tetracarboxylic acid component is added, and if necessary, stirred at room temperature to 80°C for 0.5 to 30 hours, then the temperature is raised to perform an imidization reaction, and then the dicarboxylic acid component is added, and the mixture is heated at room temperature to 80°C. A method of carrying out an amidation reaction by stirring at ℃ for 0.5 to 30 hours, (3) A tetracarboxylic acid component, a diamine component, and a reaction solvent are placed in a reactor, and the mixture is stirred at room temperature to 80℃ for 0.5 to 30 hours. and further add a dicarboxylic acid component, stir at room temperature to 80°C for 0.5 to 30 hours to perform an amidation reaction, and then raise the temperature to perform an imidization reaction, (4) diamine component and reaction solvent. is charged into a reactor and dissolved, then a tetracarboxylic acid component is charged, stirred at room temperature to 80°C for 0.5 to 30 hours as required, further added with a dicarboxylic acid component, and stirred at room temperature to 80°C as necessary. A method in which an amidation reaction is carried out by stirring at ℃ for 0.5 to 30 hours, and then the temperature is raised to carry out an imidization reaction, (5) a method in which a tetracarboxylic acid component, a diamine component, a dicarboxylic acid component, and a reaction solvent are reacted. Examples include a method in which the mixture is charged into a container, stirred for 0.5 to 30 hours at room temperature to 80° C. to carry out an amidation reaction, and then heated to carry out an imidization reaction.
ポリアミド－イミド樹脂の製造に用いられる反応溶剤は、アミド化反応及びイミド化反応を阻害せず、生成するポリアミド－イミド樹脂を溶解できるものであればよい。例えば、非プロトン性溶剤、フェノール系溶剤、エーテル系溶剤、カーボネート系溶剤等が挙げられる。 The reaction solvent used for producing the polyamide-imide resin may be any solvent as long as it does not inhibit the amidation reaction and imidization reaction and can dissolve the polyamide-imide resin produced. Examples include aprotic solvents, phenolic solvents, ether solvents, carbonate solvents, and the like.
非プロトン性溶剤の具体例としては、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン、Ｎ－メチルカプロラクタム、１，３－ジメチルイミダゾリジノン、テトラメチル尿素等のアミド系溶剤、γ－ブチロラクトン、γ－バレロラクトン等のラクトン系溶剤、ヘキサメチルホスホリックアミド、ヘキサメチルホスフィントリアミド等の含リン系アミド系溶剤、ジメチルスルホン、ジメチルスルホキシド、スルホラン等の含硫黄系溶剤、アセトン、シクロヘキサノン、メチルシクロヘキサノン等のケトン系溶剤、ピコリン、ピリジン等のアミン系溶剤、酢酸（２－メトキシ－１－メチルエチル）等のエステル系溶剤等が挙げられる。 Specific examples of aprotic solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1,3-dimethylimidazolidinone, and tetramethylurea. amide solvents, lactone solvents such as γ-butyrolactone and γ-valerolactone, phosphorus-containing amide solvents such as hexamethylphosphoric amide and hexamethylphosphine triamide, sulfur-containing solvents such as dimethylsulfone, dimethylsulfoxide, and sulfolane. Examples include ketone solvents such as acetone, cyclohexanone, and methylcyclohexanone, amine solvents such as picoline and pyridine, and ester solvents such as acetic acid (2-methoxy-1-methylethyl).
フェノール系溶剤の具体例としては、フェノール、ｏ－クレゾール、ｍ－クレゾール、ｐ－クレゾール、２，３－キシレノール、２，４－キシレノール、２，５－キシレノール、２，６－キシレノール、３，４－キシレノール、３，５－キシレノール等が挙げられる。
エーテル系溶剤の具体例としては、１，２－ジメトキシエタン、ビス（２－メトキシエチル）エーテル、１，２－ビス（２－メトキシエトキシ）エタン、ビス〔２－（２－メトキシエトキシ）エチル〕エーテル、テトラヒドロフラン、１，４－ジオキサン等が挙げられる。
また、カーボネート系溶剤の具体的な例としては、ジエチルカーボネート、メチルエチルカーボネート、エチレンカーボネート、プロピレンカーボネート等が挙げられる。
上記反応溶剤の中でも、アミド系溶剤又はラクトン系溶剤が好ましい。また、上記の反応溶剤は単独で又は２種以上混合して用いてもよい。Specific examples of phenolic solvents include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4 -xylenol, 3,5-xylenol, etc.
Specific examples of ether solvents include 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, and bis[2-(2-methoxyethoxy)ethyl]. Examples include ether, tetrahydrofuran, 1,4-dioxane and the like.
Further, specific examples of carbonate-based solvents include diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate, and the like.
Among the above reaction solvents, amide solvents or lactone solvents are preferred. Further, the above reaction solvents may be used alone or in combination of two or more.
アミド化反応及びイミド化反応では、ディーンスターク装置などを用いて、製造時に生成する水を除去しながら反応を行うことが好ましい。このような操作を行うことで、重合度及びイミド化率をより上昇させることができる。 In the amidation reaction and imidization reaction, it is preferable to use a Dean-Stark apparatus or the like to perform the reaction while removing water generated during production. By performing such an operation, the degree of polymerization and the imidization rate can be further increased.
上記のイミド化反応においては、公知のイミド化触媒を用いることができる。イミド化触媒としては、塩基触媒又は酸触媒が挙げられる。
塩基触媒としては、ピリジン、キノリン、イソキノリン、α－ピコリン、β－ピコリン、２，４－ルチジン、２，６－ルチジン、トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン、トリエチレンジアミン、イミダゾール、Ｎ，Ｎ－ジメチルアニリン、Ｎ，Ｎ－ジエチルアニリン等の有機塩基触媒、水酸化カリウムや水酸化ナトリウム、炭酸カリウム、炭酸ナトリウム、炭酸水素カリウム、炭酸水素ナトリウム等の無機塩基触媒が挙げられる。
また、酸触媒としては、クロトン酸、アクリル酸、トランス－３－ヘキセノイック酸、桂皮酸、安息香酸、メチル安息香酸、オキシ安息香酸、テレフタル酸、ベンゼンスルホン酸、パラトルエンスルホン酸、ナフタレンスルホン酸等が挙げられる。上記のイミド化触媒は単独で又は２種以上を組み合わせて用いてもよい。
上記のうち、取り扱い性の観点から、塩基触媒を用いることが好ましく、有機塩基触媒を用いることがより好ましく、トリエチルアミンを用いることが更に好ましく、トリエチルアミンとトリエチレンジアミンを組み合わせて用いることが特に好ましい。In the above imidization reaction, a known imidization catalyst can be used. Examples of imidization catalysts include base catalysts and acid catalysts.
Base catalysts include pyridine, quinoline, isoquinoline, α-picoline, β-picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine, triethylenediamine, imidazole, N,N Examples include organic base catalysts such as -dimethylaniline and N,N-diethylaniline, and inorganic base catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, and sodium hydrogen carbonate.
In addition, examples of acid catalysts include crotonic acid, acrylic acid, trans-3-hexenoic acid, cinnamic acid, benzoic acid, methylbenzoic acid, oxybenzoic acid, terephthalic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, etc. can be mentioned. The above imidization catalysts may be used alone or in combination of two or more.
Among the above, from the viewpoint of ease of handling, it is preferable to use a base catalyst, it is more preferable to use an organic base catalyst, it is even more preferable to use triethylamine, and it is particularly preferable to use a combination of triethylamine and triethylenediamine.
イミド化反応の温度は、反応率及びゲル化等の抑制の観点から、好ましくは１２０～２５０℃、より好ましくは１６０～２００℃である。また、反応時間は、生成水の留出開始後、好ましくは０．５～１０時間である。 The temperature of the imidization reaction is preferably 120 to 250°C, more preferably 160 to 200°C from the viewpoint of reaction rate and suppression of gelation and the like. Further, the reaction time is preferably 0.5 to 10 hours after the start of distillation of the produced water.
［ポリアミド－イミドワニス］
本発明のポリアミド－イミドワニスは、本発明のポリアミド－イミド樹脂が有機溶媒に溶解してなるものである。即ち、本発明のポリアミド－イミドワニスは、本発明のポリアミド－イミド樹脂及び有機溶媒を含み、当該ポリアミド－イミド樹脂は当該有機溶媒に溶解している。
有機溶媒はポリアミド－イミド樹脂が溶解するものであればよく、特に限定されないが、ポリアミド－イミド樹脂の製造に用いられる反応溶剤として上述した化合物を、単独又は２種以上を混合して用いることが好ましい。
本発明のポリアミド－イミドワニスは、重合法により得られるポリアミド－イミド樹脂が反応溶剤に溶解したポリアミド－イミド溶液そのものであってもよいし、又は当該ポリアミド－イミド溶液に対して更に希釈溶剤を追加したものであってもよい。[Polyamide-imide varnish]
The polyamide-imide varnish of the present invention is obtained by dissolving the polyamide-imide resin of the present invention in an organic solvent. That is, the polyamide-imide varnish of the present invention contains the polyamide-imide resin of the present invention and an organic solvent, and the polyamide-imide resin is dissolved in the organic solvent.
The organic solvent is not particularly limited as long as it dissolves the polyamide-imide resin, but the above-mentioned compounds can be used alone or in a mixture of two or more as a reaction solvent used in the production of the polyamide-imide resin. preferable.
The polyamide-imide varnish of the present invention may be a polyamide-imide solution itself in which a polyamide-imide resin obtained by a polymerization method is dissolved in a reaction solvent, or it may be a polyamide-imide solution itself obtained by adding a diluting solvent to the polyamide-imide solution. It may be something.
本発明のポリアミド－イミド樹脂は溶媒溶解性を有しているため、室温で安定な高濃度のワニスとすることができる。本発明のポリアミド－イミドワニスは、本発明のポリアミド－イミド樹脂を５～４０質量％含むことが好ましく、１０～３０質量％含むことがより好ましい。ポリアミド－イミドイミドワニスの粘度は１～２００Ｐａ・ｓが好ましく、５～１５０Ｐａ・ｓがより好ましい。ポリアミド－イミドワニスの粘度は、Ｅ型粘度計を用いて２５℃で測定された値である。
また、本発明のポリアミド－イミドワニスは、ポリアミド－イミドフィルムの要求特性を損なわない範囲で、無機フィラー、接着促進剤、剥離剤、難燃剤、紫外線安定剤、界面活性剤、レベリング剤、消泡剤、蛍光増白剤、架橋剤、重合開始剤、感光剤等各種添加剤を含んでもよい。
本発明のポリアミド－イミドワニスの製造方法は特に限定されず、公知の方法を適用することができる。Since the polyamide-imide resin of the present invention has solvent solubility, it can be made into a highly concentrated varnish that is stable at room temperature. The polyamide-imide varnish of the present invention preferably contains 5 to 40% by mass, more preferably 10 to 30% by mass of the polyamide-imide resin of the present invention. The viscosity of the polyamide-imide varnish is preferably 1 to 200 Pa·s, more preferably 5 to 150 Pa·s. The viscosity of the polyamide-imide varnish is a value measured at 25° C. using an E-type viscometer.
In addition, the polyamide-imide varnish of the present invention may contain inorganic fillers, adhesion promoters, release agents, flame retardants, ultraviolet stabilizers, surfactants, leveling agents, and antifoaming agents within the range that does not impair the required properties of the polyamide-imide film. , a fluorescent brightener, a crosslinking agent, a polymerization initiator, a photosensitizer, and other various additives.
The method for producing the polyamide-imide varnish of the present invention is not particularly limited, and known methods can be applied.
［ポリアミド－イミドフィルム］
本発明のポリアミド－イミドフィルムは、本発明のポリアミド－イミド樹脂を含む。したがって、本発明のポリアミド－イミドフィルムは、機械的特性、耐熱性、及び透明性に優れ、更に残留応力が低い。本発明のポリアミド－イミドフィルムが有する好適な物性値は上述の通りである。
本発明のポリアミド－イミドフィルムの製造方法には特に制限はなく、公知の方法を用いることができる。例えば、本発明のポリアミド－イミドワニスを、ガラス板、金属板、プラスチックなどの平滑な支持体上に塗布、又はフィルム状に成形した後、該ワニス中に含まれる反応溶剤や希釈溶剤等の有機溶媒を加熱により除去する方法等が挙げられる。前記支持体の表面には、必要に応じて、予め離形剤を塗布しておいてもよい。[Polyamide-imide film]
The polyamide-imide film of the present invention comprises the polyamide-imide resin of the present invention. Therefore, the polyamide-imide film of the present invention has excellent mechanical properties, heat resistance, and transparency, and further has low residual stress. The preferred physical properties of the polyamide-imide film of the present invention are as described above.
There are no particular limitations on the method for producing the polyamide-imide film of the present invention, and known methods can be used. For example, after the polyamide-imide varnish of the present invention is coated on a smooth support such as a glass plate, metal plate, or plastic or formed into a film, organic solvents such as reaction solvents and diluting solvents contained in the varnish are applied. Examples include a method of removing by heating. A release agent may be applied to the surface of the support in advance, if necessary.
ワニス中に含まれる有機溶媒を加熱により除去する方法としては、以下の方法が好ましい。即ち、１２０℃以下の温度で有機溶媒を蒸発させて自己支持性フィルムとした後、該自己支持性フィルムを支持体より剥離し、該自己支持性フィルムの端部を固定し、用いた有機溶媒の沸点以上の温度で乾燥してポリアミド－イミドフィルムを製造することが好ましい。また、窒素雰囲気下で乾燥することが好ましい。乾燥雰囲気の圧力は、減圧、常圧、加圧のいずれでもよい。自己支持性フィルムを乾燥してポリアミド－イミドフィルムを製造する際の加熱温度は、特に限定されないが、２００～４００℃が好ましい。 As a method for removing the organic solvent contained in the varnish by heating, the following method is preferable. That is, after evaporating the organic solvent at a temperature of 120° C. or lower to form a self-supporting film, the self-supporting film is peeled off from the support, the edges of the self-supporting film are fixed, and the organic solvent used is removed. It is preferable to produce a polyamide-imide film by drying at a temperature higher than the boiling point of the polyamide-imide film. Moreover, it is preferable to dry under a nitrogen atmosphere. The pressure of the drying atmosphere may be reduced pressure, normal pressure, or increased pressure. The heating temperature when drying the self-supporting film to produce a polyamide-imide film is not particularly limited, but is preferably 200 to 400°C.
また、本発明のポリアミド－イミドフィルムは、ポリアミド－アミド酸が有機溶媒に溶解してなるポリアミド－アミド酸ワニスを用いて製造することもできる。
前記ポリアミド－アミド酸ワニスに含まれるポリアミド－アミド酸は、本発明のポリアミド－イミド樹脂の前駆体であって、上述の構成単位（Ａ－１）を与える化合物を含むテトラカルボン酸成分と、上述の構成単位（Ｂ－１）を与える化合物を含むジアミン成分とが重付加反応により結合したアミド酸構造を有し、かつ上述の構成単位（Ｃ－１）を与える化合物を含むジカルボン酸成分と、上述の構成単位（Ｂ－１）を与える化合物を含むジアミン成分とがアミド結合により連結してなる構造を有する生成物である。このポリアミド－アミド酸をイミド化（脱水閉環）することで、最終生成物である本発明のポリアミド－イミド樹脂が得られる。
前記ポリアミド－アミド酸ワニスに含まれる有機溶媒としては、本発明のポリアミド－イミドワニスに含まれる有機溶媒を用いることができる。
本発明において、ポリアミド－アミド酸ワニスは、上述のテトラカルボン酸成分とジアミン成分とジカルボン酸成分との反応により得られるポリアミド－アミド酸溶液そのものであってもよいし、又は当該ポリアミド酸溶液に対して更に希釈溶剤を追加したものであってもよい。Furthermore, the polyamide-imide film of the present invention can also be produced using a polyamide-amic acid varnish prepared by dissolving polyamide-amic acid in an organic solvent.
The polyamide-amic acid contained in the polyamide-amic acid varnish is a precursor of the polyamide-imide resin of the present invention, and contains a tetracarboxylic acid component containing the compound that provides the above-mentioned structural unit (A-1), and the above-mentioned A dicarboxylic acid component having an amic acid structure bonded by a polyaddition reaction with a diamine component containing a compound that provides the structural unit (B-1), and containing a compound that provides the above-mentioned structural unit (C-1); It is a product having a structure in which a diamine component containing a compound providing the above-mentioned structural unit (B-1) is connected through an amide bond. By imidizing this polyamide-amic acid (dehydration ring closure), the final product, the polyamide-imide resin of the present invention, is obtained.
As the organic solvent contained in the polyamide-amic acid varnish, the organic solvent contained in the polyamide-imide varnish of the present invention can be used.
In the present invention, the polyamide-amic acid varnish may be the polyamide-amic acid solution itself obtained by the reaction of the above-mentioned tetracarboxylic acid component, diamine component, and dicarboxylic acid component, or Furthermore, a diluting solvent may be added.
ポリアミド－アミド酸ワニスを用いてポリアミド－イミドフィルムを製造する方法には特に制限はなく、公知の方法を用いることができる。例えば、ポリアミド－アミド酸ワニスを、ガラス板、金属板、プラスチックなどの平滑な支持体上に塗布、又はフィルム状に成形し、該ワニス中に含まれる反応溶剤や希釈溶剤等の有機溶媒を加熱により除去してポリアミド－アミド酸フィルムを得て、該ポリアミド－アミド酸フィルム中のポリアミド－アミド酸を加熱によりイミド化することで、ポリアミド－イミドフィルムを製造することができる。
ポリアミド－アミド酸ワニスを乾燥させてポリアミド－アミド酸フィルムを得る際の加熱温度としては、好ましくは５０～１２０℃である。ポリアミド－アミド酸を加熱によりイミド化する際の加熱温度としては好ましくは２００～４００℃である。
なお、イミド化の方法は熱イミド化に限定されず、化学イミド化を適用することもできる。There are no particular restrictions on the method for producing a polyamide-imide film using a polyamide-amic acid varnish, and any known method can be used. For example, a polyamide-amic acid varnish is coated on a smooth support such as a glass plate, metal plate, or plastic, or formed into a film, and the organic solvent such as the reaction solvent or diluent contained in the varnish is heated. A polyamide-imide film can be produced by removing the polyamide-amic acid film to obtain a polyamide-amic acid film, and imidizing the polyamide-amic acid in the polyamide-amic acid film by heating.
The heating temperature when drying the polyamide-amic acid varnish to obtain a polyamide-amic acid film is preferably 50 to 120°C. The heating temperature when imidizing polyamide-amic acid by heating is preferably 200 to 400°C.
Note that the imidization method is not limited to thermal imidization, and chemical imidization can also be applied.
本発明のポリアミド－イミドフィルムの厚みは用途等に応じて適宜選択することができるが、好ましくは１～１００μｍ、より好ましくは３～５０μｍ、更に好ましくは５～３０μｍの範囲である。厚みが１～１００μｍであることで、自立膜としての実用的な使用が可能となる。
ポリアミド－イミドイミドフィルムの厚みは、ポリアミド－イミドワニスの固形分濃度や粘度を調整することにより、容易に制御することができる。The thickness of the polyamide-imide film of the present invention can be appropriately selected depending on the intended use, but is preferably in the range of 1 to 100 μm, more preferably 3 to 50 μm, and still more preferably 5 to 30 μm. A thickness of 1 to 100 μm allows practical use as a self-supporting membrane.
The thickness of the polyamide-imide film can be easily controlled by adjusting the solid content concentration and viscosity of the polyamide-imide varnish.
本発明のポリアミド－イミドフィルムは、カラーフィルター、フレキシブルディスプレイ、半導体部品、光学部材等の各種部材用のフィルムとして好適に用いられる。本発明のポリアミド－イミドフィルムは、液晶ディスプレイやＯＬＥＤディスプレイ等の画像表示装置の基板として、特に好適に用いられる。 The polyamide-imide film of the present invention is suitably used as a film for various members such as color filters, flexible displays, semiconductor parts, and optical members. The polyamide-imide film of the present invention is particularly suitably used as a substrate for image display devices such as liquid crystal displays and OLED displays.
以下に、実施例により本発明を具体的に説明する。但し、本発明はこれらの実施例により何ら制限されるものではない。
実施例及び比較例で得たワニスの固形分濃度及びフィルムの各物性は以下に示す方法によって測定した。The present invention will be specifically explained below using Examples. However, the present invention is not limited to these Examples in any way.
The solid content concentration of the varnishes obtained in Examples and Comparative Examples and the physical properties of the films were measured by the methods shown below.
（１）固形分濃度
ワニスの固形分濃度の測定は、アズワン株式会社製の小型電気炉「ＭＭＦ－１」で試料を３２０℃×１２０ｍｉｎで加熱し、加熱前後の試料の質量差から算出した。
（２）フィルム厚さ
フィルム厚さは、株式会社ミツトヨ製のマイクロメーターを用いて測定した。
（３）引張弾性率、引張強度
引張弾性率及び引張強度は、ＪＩＳ Ｋ７１２７に準拠し、東洋精機株式会社製の引張試験機「ストログラフＶＧ－１Ｅ」を用いて測定した。チャック間距離は５０ｍｍ、試験片サイズは１０ｍｍ×５０ｍｍ、試験速度は２０ｍｍ／ｍｉｎとした。引張弾性率及び引張強度は、いずれも数値が大きいほど、機械的特性に優れる。
（４）ガラス転移温度（Ｔｇ）
株式会社日立ハイテクサイエンス製の熱機械的分析装置「ＴＭＡ／ＳＳ６１００」を用いて、引張モードで試料サイズ２ｍｍ×２０ｍｍ、荷重０．１Ｎ、昇温速度１０℃／ｍｉｎの条件で、残留応力を取り除くのに十分な温度まで昇温して残留応力を取り除き、その後室温まで冷却した。その後、前記残留応力を取り除くための処理と同じ条件で試験片伸びの測定の測定を行い、伸びの変曲点が見られたところをガラス転移温度として求めた。Ｔｇは数値が大きいほど、耐熱性に優れる。
（５）全光線透過率
全光線透過率は、ＪＩＳ Ｋ７３６１－１：１９９７に準拠し、日本電色工業株式会社製の色彩・濁度同時測定器「ＣＯＨ４００」を用いて測定した。全光線透過率は１００％に近いほど、透明性に優れる。
（６）残留応力
ケーエルエー・テンコール社製の残留応力測定装置「ＦＬＸ－２３２０」を用いて、予め「反り量」を測定しておいた、厚み５２５μｍ±２５μｍの４インチシリコンウェハ上に、ポリアミド－イミドワニスあるいはポリアミド－アミド酸ワニスを、スピンコーターを用いて塗布し、プリベークした。その後、熱風乾燥器を用いて、窒素雰囲気下、３５０℃３０分の条件下で加熱処理を施し、加熱後膜厚８～２０μｍのポリアミド－イミドフィルムのついたシリコンウェハを作製した。このウェハの反り量を前述の残留応力測定装置を用いて測定し、シリコンウェハとポリアミド－イミドフィルムの間に生じた残留応力を評価した。(1) Solid content concentration The solid content concentration of the varnish was measured by heating the sample at 320°C x 120 min in a small electric furnace "MMF-1" manufactured by As One Co., Ltd., and calculating from the difference in mass of the sample before and after heating.
(2) Film thickness The film thickness was measured using a micrometer manufactured by Mitutoyo Co., Ltd.
(3) Tensile modulus and tensile strength The tensile modulus and tensile strength were measured using a tensile tester "Strograph VG-1E" manufactured by Toyo Seiki Co., Ltd. in accordance with JIS K7127. The distance between chucks was 50 mm, the test piece size was 10 mm x 50 mm, and the test speed was 20 mm/min. The larger the tensile modulus and tensile strength are, the better the mechanical properties are.
(4) Glass transition temperature (Tg)
Using a thermomechanical analyzer "TMA/SS6100" manufactured by Hitachi High-Tech Science Co., Ltd., remove residual stress in tensile mode under the conditions of sample size 2 mm x 20 mm, load 0.1 N, and temperature increase rate 10 ° C / min. The temperature was raised to a temperature sufficient to remove residual stress, and then cooled to room temperature. Thereafter, the elongation of the test piece was measured under the same conditions as the treatment for removing the residual stress, and the point where the inflection point of elongation was found was determined as the glass transition temperature. The larger the value of Tg, the better the heat resistance.
(5) Total light transmittance The total light transmittance was measured in accordance with JIS K7361-1:1997 using a simultaneous color and turbidity meter "COH400" manufactured by Nippon Denshoku Industries Co., Ltd. The closer the total light transmittance is to 100%, the better the transparency.
(6) Residual stress Polyamide- An imide varnish or a polyamide-amic acid varnish was applied using a spin coater and prebaked. Thereafter, heat treatment was performed using a hot air dryer at 350° C. for 30 minutes in a nitrogen atmosphere to produce a silicon wafer with a polyamide-imide film having a thickness of 8 to 20 μm after heating. The amount of warpage of this wafer was measured using the residual stress measuring device described above, and the residual stress generated between the silicon wafer and the polyamide-imide film was evaluated.
実施例及び比較例にて使用したテトラカルボン酸成分、ジカルボン酸成分及びジアミン成分、並びにその略号は以下の通りである。
＜テトラカルボン酸成分＞
ＣｐＯＤＡ：ノルボルナン－２－スピロ－α－シクロペンタノン－α’－スピロ－２’’－ノルボルナン－５，５’’，６，６’’－テトラカルボン酸二無水物（ＪＸエネルギー株式会社製；式（ａ－１）で表される化合物）
ＢＰＤＡ：３，３’，４，４’－ビフェニルテトラカルボン酸二無水物（三菱ケミカル株式会社製；式（ａ－２）で表される化合物）
＜ジカルボン酸成分＞
ＴＰＣ：テレフタル酸クロリド（東京化成工業株式会社製；式（ｃ－１）で表される化合物）
＜ジアミン＞
ＴＦＭＢ：２，２’－ビス（トリフルオロメチル）ベンジジン（セイカ株式会社製；式（ｂ－１）で表される化合物）The tetracarboxylic acid component, dicarboxylic acid component, and diamine component used in Examples and Comparative Examples, and their abbreviations are as follows.
<Tetracarboxylic acid component>
CpODA: norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride (manufactured by JX Energy Corporation; Compound represented by formula (a-1))
BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride (manufactured by Mitsubishi Chemical Corporation; compound represented by formula (a-2))
<Dicarboxylic acid component>
TPC: Terephthalic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.; compound represented by formula (c-1))
<Diamine>
TFMB: 2,2'-bis(trifluoromethyl)benzidine (manufactured by Seika Co., Ltd.; compound represented by formula (b-1))
＜実施例１＞
ステンレス製半月型撹拌翼、窒素導入管、冷却管を取り付けたディーンスターク、温度計、ガラス製エンドキャップを備えた１Ｌの５つ口丸底フラスコに、ＴＦＭＢ３２．０２４ｇ（０．１００モル）、Ｎ－メチル－２－ピロリドン（三菱ケミカル株式会社製）６３．５７０ｇを投入し、系内温度７０℃、窒素雰囲気下、回転数２００ｒｐｍで撹拌して溶液を得た。
この溶液に、ＣｐＯＤＡ２６．９０７ｇ（０．０７０モル）、及びＮ－メチル－２－ピロリドン（三菱ケミカル株式会社製）１５．８９４ｇを一括で添加した後、イミド化触媒としてトリエチルアミン（関東化学株式会社製）０．３５４ｇ及びトリエチレンジアミン（東京化成工業株式会社製）０．０３９ｇを投入し、マントルヒーターで加熱し、約２０分かけて反応系内温度を１９０℃まで上げた。留去される成分を捕集し、回転数を粘度上昇に合わせて調整しつつ、反応系内温度を１９０℃に保持して２時間還流した。
その後、Ｎ－メチル－２－ピロリドン（三菱ケミカル株式会社製）２６８．５６０ｇを添加して、反応系内温度を１２０℃まで冷却した後、更に約３時間撹拌して均一化し、固形分濃度１５質量％のポリイミドワニスを得た。続いてＴＰＣ６．０９１ｇ（０．０３０モル）、Ｎ－メチル－２－ピロリドン（三菱ケミカル株式会社製）２０４．７０ｇを投入し、系内温度５０℃、窒素雰囲気下、回転数２００ｒｐｍで２時間撹拌してポリアミド－イミドワニスを得た。
その後、ポリアミド－イミドワニスをＮ－メチル－２－ピロリドン（三菱ケミカル株式会社製）にて固形分濃度５．０質量％に希釈し、大過剰のメタノールに滴下することでポリアミド－イミド粉体を沈殿させた。その後、桐山ロートにより吸引ろ過し、大過剰のメタノール、イオン交換水で各２回洗浄した。桐山ロートにより吸引ろ過し窒素雰囲気下、２００℃で２時間乾燥させることでポリアミド－イミド粉体を得た。
ポリアミド－イミド粉体５．０００ｇをＮ－メチル－２－ピロリドン（三菱ケミカル株式会社製）４５．０００ｇに溶解し固形分濃度１０．０質量％のポリアミド－イミドワニスを得た。
その後、ガラス、あるいはシリコンウェハ上へ、得られたポリアミド－イミドワニスを塗布し、ホットプレートで８０℃、２０分間保持し、その後、窒素雰囲気下、熱風乾燥機中３５０℃で３０分加熱し溶媒を蒸発させ、厚み８μｍのフィルムを得た。結果を表１に示す。<Example 1>
32.024 g (0.100 mol) of TFMB, N was placed in a 1 L 5-necked round-bottomed flask equipped with a stainless steel half-moon stirring blade, a nitrogen inlet tube, a Dean Stark equipped with a cooling tube, a thermometer, and a glass end cap. -Methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical Corporation) (63.570 g) was added, and the system was stirred at a rotational speed of 200 rpm under a nitrogen atmosphere at a system temperature of 70° C. to obtain a solution.
To this solution, 26.907 g (0.070 mol) of CpODA and 15.894 g of N-methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical Corporation) were added all at once, and then triethylamine (manufactured by Kanto Chemical Co., Ltd.) was added as an imidization catalyst. ) and 0.039 g of triethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and heated with a mantle heater to raise the temperature inside the reaction system to 190° C. over about 20 minutes. The components to be distilled off were collected, and the reaction system was refluxed for 2 hours while the internal temperature of the reaction system was maintained at 190° C. while adjusting the rotation speed according to the increase in viscosity.
Thereafter, 268.560 g of N-methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical Corporation) was added, and the temperature inside the reaction system was cooled to 120°C, followed by further stirring for about 3 hours to homogenize the solid content to 15. A polyimide varnish of % by mass was obtained. Subsequently, 6.091 g (0.030 mol) of TPC and 204.70 g of N-methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical Corporation) were added, and the mixture was stirred for 2 hours at a system temperature of 50°C and a rotational speed of 200 rpm under a nitrogen atmosphere. A polyamide-imide varnish was obtained.
Then, the polyamide-imide varnish was diluted with N-methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical Corporation) to a solid content concentration of 5.0% by mass, and the polyamide-imide powder was precipitated by dropping it into a large excess of methanol. I let it happen. Thereafter, it was suction-filtered using a Kiriyama funnel, and washed twice each with large excess methanol and ion-exchanged water. A polyamide-imide powder was obtained by suction filtration using a Kiriyama funnel and drying at 200° C. for 2 hours in a nitrogen atmosphere.
5.000 g of polyamide-imide powder was dissolved in 45.000 g of N-methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical Corporation) to obtain a polyamide-imide varnish with a solid content concentration of 10.0% by mass.
Thereafter, the resulting polyamide-imide varnish was applied onto a glass or silicon wafer, kept at 80°C for 20 minutes on a hot plate, and then heated at 350°C for 30 minutes in a hot air dryer under a nitrogen atmosphere to remove the solvent. After evaporation, a film with a thickness of 8 μm was obtained. The results are shown in Table 1.
＜実施例２＞
ＣｐＯＤＡ２６．９０７ｇ（０．０７０モル）から１５．３７５ｇ（０．０４０モル）に変更し、ＣｐＯＤＡ添加と同時にＢＰＤＡを８．８２６ｇ（０．０３０モル）追加で投入した以外は実施例１と同様の方法によりポリアミド－イミドワニスを作製し、固形分濃度１０．０質量％のポリアミド－イミドワニスを得た。
得られたポリアミド－イミドワニスを用いて、実施例１と同様の方法によりフィルムを作製し、厚み９μｍのフィルムを得た。結果を表１に示す。<Example 2>
Same as Example 1 except that 26.907 g (0.070 mol) of CpODA was changed to 15.375 g (0.040 mol) and 8.826 g (0.030 mol) of BPDA was added at the same time as CpODA addition. A polyamide-imide varnish was produced by the method, and a polyamide-imide varnish with a solid content concentration of 10.0% by mass was obtained.
Using the obtained polyamide-imide varnish, a film was produced in the same manner as in Example 1 to obtain a film with a thickness of 9 μm. The results are shown in Table 1.
＜比較例１＞
ステンレス製半月型撹拌翼、窒素導入管、冷却管を取り付けたディーンスターク、温度計、ガラス製エンドキャップを備えた１Ｌの５つ口丸底フラスコに、ＴＦＭＢ３２．０２４ｇ（０．１００モル）、Ｎ－メチル－２－ピロリドン（三菱ケミカル株式会社製）８４．５５４ｇを投入し、系内温度７０℃、窒素雰囲気下、回転数２００ｒｐｍで撹拌して溶液を得た。
この溶液に、ＣｐＯＤＡ３８．４３８ｇ（０．１００モル）、及びＮ－メチル－２－ピロリドン（三菱ケミカル株式会社製）２１．１３９ｇを一括で添加した後、イミド化触媒としてトリエチルアミン（関東化学株式会社製）０．５０６ｇ及びトリエチレンジアミン（東京化成工業株式会社製）０．０５６ｇを投入し、マントルヒーターで加熱し、約２０分かけて反応系内温度を１９０℃まで上げた。留去される成分を捕集し、回転数を粘度上昇に合わせて調整しつつ、反応系内温度を１９０℃に保持して３時間還流した。
その後、Ｎ－メチル－２－ピロリドン（三菱ケミカル株式会社製）４９６．０２９ｇを添加して、反応系内温度を１２０℃まで冷却した後、更に約３時間撹拌して均一化し、固形分濃度１０質量％のポリイミドワニスを得た。
その後、ガラス、あるいはシリコンウェハ上へ、得られたポリイミドワニスを塗布し、ホットプレートで８０℃、２０分間保持し、その後、窒素雰囲気下、熱風乾燥機中４００℃で３０分加熱し溶媒を蒸発させ、厚み１４μｍのフィルムを得た。結果を表１に示す。<Comparative example 1>
32.024 g (0.100 mol) of TFMB, N was placed in a 1 L 5-necked round-bottomed flask equipped with a stainless steel half-moon stirring blade, a nitrogen inlet tube, a Dean Stark equipped with a cooling tube, a thermometer, and a glass end cap. -Methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical Corporation) (84.554 g) was added, and the system was stirred at a rotational speed of 200 rpm at a system temperature of 70°C under a nitrogen atmosphere to obtain a solution.
To this solution, 38.438 g (0.100 mol) of CpODA and 21.139 g of N-methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical Corporation) were added all at once, and then triethylamine (manufactured by Kanto Chemical Co., Ltd.) was added as an imidization catalyst. ) and 0.056 g of triethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and heated with a mantle heater to raise the temperature inside the reaction system to 190° C. over about 20 minutes. The components to be distilled off were collected, and the reaction system was refluxed for 3 hours while maintaining the internal temperature at 190° C. while adjusting the rotation speed in accordance with the increase in viscosity.
Thereafter, 496.029 g of N-methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical Corporation) was added, and the temperature inside the reaction system was cooled to 120°C, and the mixture was further stirred for about 3 hours to homogenize. A polyimide varnish of % by mass was obtained.
Thereafter, the obtained polyimide varnish is applied onto glass or silicon wafer, held at 80℃ for 20 minutes on a hot plate, and then heated at 400℃ for 30 minutes in a hot air dryer under a nitrogen atmosphere to evaporate the solvent. A film with a thickness of 14 μm was obtained. The results are shown in Table 1.
表１に示すように、実施例１及び２のポリアミド－イミドフィルムは、機械的特性、耐熱性、及び透明性に優れ、更に残留応力の低減を達成できることが分かる。
一方、ジカルボン酸成分を使用せず、テトラカルボン酸成分としてＣｐＯＤＡのみを使用して製造した比較例１のポリイミドフィルムは、実施例１及び２のポリアミド－イミドフィルムと対比して、透明性に優れるものの、機械的特性、及び耐熱性に劣り、更に残留応力が高いことから、残留応力の低減を達成できないことが分かる。As shown in Table 1, it can be seen that the polyamide-imide films of Examples 1 and 2 have excellent mechanical properties, heat resistance, and transparency, and can further reduce residual stress.
On the other hand, the polyimide film of Comparative Example 1 produced using only CpODA as the tetracarboxylic acid component without using the dicarboxylic acid component has excellent transparency compared to the polyamide-imide films of Examples 1 and 2. However, the mechanical properties and heat resistance are poor, and the residual stress is high, so it can be seen that reduction of the residual stress cannot be achieved.
Claims (6)
構成単位Ａが下記式（ａ－１）で表される化合物に由来する構成単位（Ａ－１）を含み、
構成単位Ｂが下記式（ｂ－１）で表される化合物に由来する構成単位（Ｂ－１）を含み、
構成単位Ｃが下記式（ｃ－１）で表される化合物に由来する構成単位（Ｃ－１）を含み、
構成単位Ａ及び構成単位Ｃの合計中における構成単位（Ａ－１）の比率が３５モル％以上であり、
構成単位Ｂ中における構成単位（Ｂ－１）の比率が５０モル％以上であり、
構成単位Ａ及び構成単位Ｃの合計中における構成単位（Ｃ－１）の比率が１０～３０モル％であり、
構成単位Ｃ中における構成単位（Ｃ－１）の比率が７０モル％以上であり、
上記ポリアミド－イミド樹脂が構成単位Ｃと構成単位Ｂとがアミド結合してなる構造を含む、ポリアミド－イミド樹脂。
The structural unit A contains a structural unit (A-1) derived from a compound represented by the following formula (a-1),
Structural unit B includes a structural unit (B-1) derived from a compound represented by the following formula (b-1),
The structural unit C includes a structural unit (C-1) derived from a compound represented by the following formula (c-1),
The ratio of the structural unit (A-1) in the total of the structural units A and C is 35 mol% or more,
The ratio of the structural unit (B-1) in the structural unit B is 50 mol% or more,
The ratio of the structural unit (C-1) in the total of the structural units A and C is 10 to 30 mol%,
The ratio of the structural unit (C-1) in the structural unit C is 70 mol% or more,
A polyamide-imide resin, wherein the polyamide-imide resin has a structure in which a structural unit C and a structural unit B are bonded by an amide bond.
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| KR101870341B1 (en) | 2013-12-26 | 2018-06-22 | 코오롱인더스트리 주식회사 | Colorless Polyamide―imide Resin and Film Thereof |
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| WO2014046064A1 (en) | 2012-09-18 | 2014-03-27 | 宇部興産株式会社 | Polyimide precursor, polyimide, polyimide film, varnish, and substrate |
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